Mercury compound-specific stable isotope fractionation in high-altitude lake ecosystems of the Bolivian Altiplano

A combination of mercury (Hg) speciation and compound-specific stable isotope analyses was employed to trace the origin and fate of monomethylmercury (MMHg) in the high-altitude food webs of Lakes Titicaca (TTKK) and Uru Uru (UU). Significant MMHg biomagnification was observed, with concentrations reaching up to 2 μg.g⁻¹ Hg in top predators. Hg isotopes lake-specific trends were identified in relation to trophic position (δ¹⁵N) and MMHg fractions. In particular, Δ¹⁹⁹MMHg increased from 0 ‰ in UU epiphytic biofilm to ≈2 ‰ and ≈4 ‰ in UU and TTKK piscivorous fish, respectively. Both δ²⁰²MMHg and Δ¹⁹⁹MMHg signatures indicate that the sediment and/or the epibenthic environment is the primary MMHg source in both food webs. However, an additional MMHg pool, associated with photodegraded MMHg, was identified entering the two food webs at a different trophic level. Photodemethylation was estimated to account for 21 % of MMHg degradation before it entered TTKK Lake food web at the fish level, and 16 % before reaching UU Lake food web at the invertebrate level. Even-Hg MIF (Δ²⁰⁰Hg) shows that both Hg(0) atmospheric deposition and geogenic inputs contributed to Hg accumulation in sediments, while the food web adds significant atmospheric Hg(II) signatures, with up to 94 % of Hg(II) contributing to Lake TTKK fish MMHg. These findings underscore the high potential of Hg-CSIA revealing the dominant role of atmospheric Hg(II) deposition and distinct MMHg pools in driving MMHg bioaccumulation in high-altitude lake food webs.